Thin film capacitor having multi-layer dielectric film including silicon dioxide and tantalum pentoxide

ABSTRACT

A capacitor and a method of forming the same, one embodiment of which includes depositing a multi-layer dielectric film between first and second spaced-apart electrodes. The multi-layer dielectric film includes first and second layers that have differing roughness. The layer of the dielectric film having the least amount of roughness is disposed adjacent to the first electrode. After depositing the second layer of the dielectric film adjacent to the first layer, the second layer is annealed. An exemplary embodiment of the thin film capacitor forms the dielectric material from silicon dioxide (SiO 2 ) and tantalum pentoxide (Ta 2 O 5 ).

FIELD OF THE INVENTION

[0001] The present invention relates to a method for manufacturing asemiconductor thin film capacitor. More particularly, the presentinvention is directed to a method for manufacturing a thin filmcapacitor having a dielectric film formed of tantalum oxide.

BACKGROUND OF THE INVENTION

[0002] The operational characteristics of thin film capacitors becomeincreasingly important as the operation frequency of the variouscircuits in which these capacitors are included increases. Examples ofsuch circuits include dynamic random access memories, in which thethin-film capacitor is employed as a storage cell; filters, in which thethin-film capacitor forms part of an RC network; and multi-chip modules,in which the thin-film capacitor is employed as a decoupling capacitor.

[0003] Operational characteristics that are desirable for a thin-filmcapacitor include high-capacitance density, low current leakage and ahigh breakdown voltage. In addition, it is desirable that the capacitorsbe compatible with subsequent steps during manufacturing of the circuit.

[0004] Due to its excellent dielectric properties, extensive effortshave been made to make capacitors using Tantalum Pentoxide (Ta₂O₅) filmsdeposited by reactive sputtering, chemical vapor deposition (CVD), andplasma enhanced chemical vapor deposition. As described in U.S. Pat. No.6,235,572 to Kunitomo et al., tantalum pentoxide films are generallydeposited in an amorphous state. To improve the dielectric constant ofthe tantalum pentoxide, the films are subjected to a thermal treatmentto give the film a crystalline structure. The crystalline structure oftantalum pentoxide films present a thin poly-crystal film having a grainboundary that is subject to current leakage between electrodes disposedon opposite sides thereof. Although increasing the film thickness mayreduce the leakage current and increase the capacitance, too great anincrease exacerbates leakage current due to the increased stress itplaces on the tantalum pentoxide film. To reduce current leakage whilemaintaining sufficient capacitance, Kunitomo et al. advocate forming amulti-layered tantalum pentoxide film employing CVD techniques.

[0005] U.S. Pat. No. 5,936,831 to Kola et al., recognizes thatcapacitors fabricated with anodized reactively sputtered Ta₂O₅ filmswere found to have satisfactory leakage and breakdown properties, butdegraded upon thermal annealing above 200° C. The degradationdemonstrated irreversible increases in the temperature coefficient ofcapacitance (TCC), as well as the dissipation factor. These are believedto be caused by diffusion of electrode metal atoms into the dielectricand diffusion of oxygen out, creating oxygen deficiency defects. Toovercome this degradation, Kola et al. discuss using a variety of metalsfor the electrodes, including aluminum (Al), chromium (Cr), copper (Cu),tantalum nitride (TaN_(x)), titanium nitride (TiN_(x)) and tungsten (W).As a result, Kola et al. advocate forming a thin-film capacitor with adielectric formed from nitrogen or silicon-doped tantalum oxide and atleast one electrode formed from chromium by anodically oxidizing TaN orTa₂Si and forming a Cr electrode.

[0006] U.S. Pat. No. 6,207,489 to Nam et al., discloses a method formanufacturing a capacitor having a dielectric film formed from tantalumoxide. The method includes forming a lower electrode that iselectrically connected to an active region of a semiconductor substrate.A pre-treatment film including a component selected from a groupconsisting of silicon oxide, silicon nitride, and combinations thereof,is formed on the surface of the lower electrode. A dielectric film isformed on the pre-treatment film using a Ta precursor. The dielectricfilm includes a first dielectric layer deposited at a first temperature,which is selected from a designated temperature range. A seconddielectric layer is deposited at a second temperature, which isdifferent from the first temperature. A thermal treatment is thereafterperformed on the dielectric film in an oxygen atmosphere.

[0007] There is a need, therefore, to provide a technique for producingthin film capacitors having sufficient capacitance and break downvoltage, while minimizing current leakage.

SUMMARY OF THE INVENTION

[0008] A capacitor and a method of forming the same is disclosed, oneembodiment of which includes depositing a multi-layer dielectric filmbetween first and second spaced-apart electrodes. The multi-layerdielectric film includes first and second layers that have differingroughness. The layer of the dielectric film having the least amount ofroughness is disposed adjacent to the first electrode. After depositingthe second layer of the dielectric film adjacent to the first layer, thesecond layer is annealed. It is believed that the reduced roughness ofthe first layer reduces pin-hole formation in the second layer. In thismanner, current leakage is prevented, or reduced, in the resultingthin-film capacitor, while providing suitable capacitance and breakdownvoltage. An exemplary embodiment of the thin-film capacitor forms thedielectric material from silicon dioxide (SiO₂) and tantalum pentoxide(Ta₂O₅). To provide the thin-film capacitor with the desired operationalcharacteristics, the layer of tantalum pentoxide is provided with athickness that is approximately three times greater than the thicknessof the silicon dioxide layer. To that end, in the exemplary method, thefirst electrode is formed by vapor deposition of phosphorousoxytrichloride (POCl₃). The layer of silicon dioxide is formed bythermal oxidation of silicon in oxygen. The layer of tantalum pentoxideis formed by sputtering tantalum (Ta) onto the layer of silicon dioxidein an oxygen rich ambient. Annealing then densities the tantalum oxide.Thereafter, the second electrode is formed by deposition of a layerconsisting of aluminum, chromium, copper, titanium, titanium nitride,titungsten or a combination thereof.

[0009] These and other embodiments of the present invention, along withmany of its advantages and features, are described in more detail in thetext below and the attached figures.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010]FIG. 1 is a cross-sectional view of an exemplary thin-filmcapacitor in accordance with the present invention;

[0011]FIG. 2 is a cross-sectional view of a substrate, having a thermaloxide layer thereon, upon which the thin-film capacitor of FIG. 1 isfabricated;

[0012]FIG. 3 is a cross-sectional view of the substrate shown in FIG. 2with a section of the oxide layer removed;

[0013]FIG. 4 is a cross-sectional view of the substrate shown in FIG. 3showing diffused phosphorus region of the substrate;

[0014]FIG. 5 is a cross-sectional view of the substrate shown in FIG. 4with a multi-layer dielectric film disposed adjacent to the phosphorousdiffusion region;

[0015]FIG. 6 is a cross-sectional view of the substrate shown in FIG. 5showing a via etched therein, which extends through the dielectric andterminates proximate to the phosphorus diffusion region;

[0016]FIG. 7 is a cross-sectional view of the substrate shown in FIG. 6with a contact and additional electrode formed thereon; and

[0017]FIG. 8 is a cross-sectional view of the substrate shown in FIG. 7with a layer of Benzocyclobutene (BCB) disposed atop of the contact,additional electrode and the dielectric film.

DETAILED DESCRIPTION

[0018]FIG. 1 is a-cross-sectional view of an exemplary thin-filmcapacitor 10 in accordance with the present invention that is formedatop of a substrate 12. Capacitor 10 includes a pair of spaced-apartelectrodes 14 and 16, with a multi-layer dielectric film 18 disposedtherebetween. A via 20 is formed through dielectric film 18 and extendsfrom a surface 19 thereof, terminating proximate to electrode 14. Aconductive contact 22 is formed in via 20 so as to extend from electrode14 away from surface 24 of dielectric material 18. Contact 22 is formedadjacent to, but spaced-apart from, electrode 16. Formed adjacent to thecapacitive structure is a dielectric layer that is typically formed froma layer of Benzocyclobutene (BCB), shown as BCB layer 26. First andsecond throughways 28 and 30 are formed in BCB layer 26. Firstthroughway 28 extends from an upper surface 32 of BCB layer 26,terminating proximate to the contact 22, and second throughway 30extends from upper surface 32, terminating proximate to electrode 16. Afirst metal interconnect 34 is formed in first throughway 28 and is inelectrical communication with contact 22. A second metal interconnect 36is formed in second throughway 30 and is in electricalcommunication-with electrode 16.

[0019] In one example of capacitor 10, electrode 14 is formed from aconductive layer of diffused phosphorus. Electrode 16, contact 22 andmetal interconnects 34 and 36 may be formed from any conductive materialknown in the semiconductor processing art, including aluminum (Al),chromium (Cr), copper (Cu), titanium (Ti), titanium nitride (TiN),tungsten (W), titungsten (TiW) or a combination thereof.

[0020] To provide superior operational characteristics of capacitor 10,dielectric film 18 includes a layer 18 a of tantalum pentoxide (Ta₂O₅).Dielectric film 18 is formed as a multi-layer structure to overcome aproblem encountered when manufacturing capacitor 10. Specifically, toachieve the desired capacitance and breakdown voltage with minimalleakage between the capacitor electrodes, it is beneficial to have aninterfacial film between the silicon and the tantalum oxide. It isdesired that this interfacial film have good integrity and a very smoothinterface in the transition region. Thermal silicon oxide satisfies bothof these requirements. It is a high integrity film with a very low pinhole density and minimal surface roughness at both the interface and theexposed top surface. These silicon oxide characteristics enable thesputter deposition of a high quality tantalum oxide film on the surfaceof the oxide film. The presence of a thin, dense, high quality, oxidefilm at the silicon interface will increase the capacitor breakdownvoltage, and reduce the capacitor leakage current.

[0021] It is believed that the current leakage is due, in part, to theroughness of the grain boundary of tantalum pentoxide layer upon beingdensified by annealing. To overcome this problem dielectric film 18includes a second layer of dielectric material, such as silicon dioxide(SiO₂) layer 18 b. Silicon dioxide layer 18 b is employed, because ithas a roughness that is less than tantalum pentoxide layer 18 a. It isbelieved that the reduced roughness presented by silicon dioxide layer18 b substantially reduces pin hole formation in the dielectric layer18. As a result, the current leakage of the capacitor 10 issubstantially reduced, if not eliminated. To maintain the advantageouscharacteristics provided by tantalum pentoxide layer 18 a, it isdesirable to minimize the thickness of silicon dioxide layer 18 b. Tothat end, one embodiment of capacitor 10 provides a portion 18 c oftantalum pentoxide layer 18 a that superimposes silicon dioxide layer 18b with a thickness at least three time greater than the thickness ofsilicon dioxide layer 18 b.

[0022] In an exemplary embodiment of capacitor 10, silicon dioxide layer18 b is approximately 50 Å thick and tantalum pentoxide layer 18 a isapproximately 150 Å thick. Electrode 14 is formed from athree-micron-deep diffusion of phosphorus providing a sheet resistivityof 2-3 ohms/cm². Electrode 16 and contact 22 are formed from one micronaluminum disposed atop of a titanium nitride layer barrier layer (notshown) BCB layer 26 is approximately 3 microns thick. Metalinterconnects 34 and 36 are formed from copper with an adhesion filmcomposed of either titanium, chrome, or titungsten (TiW). With thisconfiguration capacitor 10 demonstrated a capacitance of approximately270 to 300 nanofarad/cm² and a breakdown voltage in excess of 7 volts,with minimum current leakage.

[0023] Referring to FIGS. 1 and 2, the fabrication of capacitor 10involves forming a thermal oxide layer 40 on substrate 12. Althoughsubstrate 12 may be formed from any suitable semiconductor material, inthe present example substrate 12 is formed from silicon (Si). Therefore,the oxide layer comprises of silicon dioxide. Typically, the oxide layeris approximately 20,000 to 30,000 Å thick.

[0024] Referring to FIGS. 1 and 3, a resist pattern (not shown) isdisposed onto oxide layer 40, and an etching process is employed toremove an area of oxide layer 40, exposing a portion 42 on the surfaceof substrate 12, to facilitate formation of electrode 14. A bufferedoxide etch (BOE) hydrofluoric acid etch process is an exemplarytechnique employed to remove the area of oxide layer 40, to exposeportion 42. In such a process, the pattern oxide layer 40 is exposed tothe BOE (buffered oxide etch) hydrofluoric acid etch for approximately30 minutes. Thereafter, the resist (not shown) is removed and aphosphorus rich glass is grown on oxide layer 40 and and portion 42 viathe reaction between POCl₃ and O₂ in the hot diffusion tube by chemicalvapor deposition.

[0025] Referring to FIGS. 1 and 4, after formation of the phosphorusrich glass on the surface of portions 40 and 42, the substrate isthermally baked-at approximately 1000° C. for approximately two hours.This results in diffusion of the phosphorus from the phosphorus richglass into a region 44 of substrate 12, thereby forming electrode 14.Electrode 14 is approximately three microns deep and extends completelyover region 44 and partially under oxide layer 40 at the edge of theopening. Thereafter, the structure of FIG. 3 is exposed to ahydrofluoric acid (HF) solution to remove the surface rich phosphorusglass oxide that was the source for the phosphorus diffusion to form thebottom electrode. The concentration of hydrofluoric acid is 10:1, i.e.,ten parts water to one part hydrofluoric acid.

[0026] Referring to FIGS. 1 and 5, after removal of the phosphorus richglass oxide with hydrofluoric acid, a layer of silicon dioxide 18 b isthermally grown adjacent to the exposed surfaces of oxide layer 40 andregion 44 via thermal oxidation of the exposed silicon. Specifically,layer 18 b is grown in an environment of oxygen gas at approximately850° C. to grow a 30-50 Å SiO₂ film. After thermal oxidation to form the30-50 Å silicon dioxide layer 18 b on the surface of region 44, tantalummetal is sputtered in an oxygen rich ambient in the sputter chamber toform a layer of tantalum pentoxide (Ta₂O₅) 18 a. Tantalum pentoxidelayer 18 a has a thickness, in an area thereof that is coextensive withregion 44, in the range of 90 to 150 Å. Tantalum pentoxide layer 18 a isdensified by subjecting the structure of FIG. 5 to temperatures in arange of 750° C. to 900° C. in a 20% oxygen/nitrogen mixture, therebyforming a multi-layer dielectric film composed of thermal oxide (SiO₂)18 b, and tantalum pentoxide (Ta₂O₅) 18 a.

[0027] Referring to FIGS. 1 and 6, a mask (not shown) is disposed upontantalum pentoxide layer 18 a in preparation to form a via 50 employinga plasma etch process utilizing a fluorine plasma chemistry, i.e. CHF₃,SF₆, etc. This is followed by removal of the mask and subsequentdeposition of a barrier film (not shown) formed from titanium nitride.Thereafter, an aluminum or copper layer is deposited, patterned byresist lithography, and etched to form contact 22 and electrode 16,shown in FIG. 7. After removal of resist, the barrier film in the fieldarea is removed with a fluorine plasma etch. After removal of thebarrier film in the field area a photosensitive film of BCB(Benzocyclobutene) is applied to the surface of the wafer. As shown inFIG. 8, BCB layer 26 is exposed and developed to form the via contacts28 and 30 (throughways) to the top and bottom capacitor electrodes. BCBlayer 26 is then semicured at a temperature of 210° C. in a nitrogenambient. Following the BCB semicure a metal adhesion film (not shown)and a conductive metal film (not shown) are deposited and the metalpattern defined with standard photoresist lithography. The developedphotoresist pattern is hard baked and the metal etched, thereby formingconductive interconnects 34 and 36. The resist (not shown) employed forthe pattern is then removed.

[0028] Although the invention has been described in terms of specificembodiments, these embodiments are exemplary. Variations may be made tothe embodiments as disclosed and still be within the scope of theinvention. The invention should not be determined, therefore, basedsolely upon the foregoing description. Rather, the invention should bedetermined based upon the attached claims, including the full scope ofequivalents thereof.

What is claimed is:
 1. A method for manufacturing a capacitor on asemiconductor substrate, said method comprising: forming a firstelectrode by depositing a conductive layer on said substrate; depositinga multi-layer dielectric film adjacent to said first electrode, withsaid dielectric film including first and second layers, said first layerbeing disposed adjacent to said first electrode and having a roughnessassociated therewith that is less than a roughness associated with saidsecond layer; and forming a second electrode by depositing an additionalconductive layer adjacent to said second layer.
 2. The method as recitedin claim 1 wherein depositing said dielectric film further includesgrowing said first layer by thermal oxidation to form silicon dioxide.3. The method as recited in claim 1 wherein said first layer consists ofa layer of silicon dioxide and said second layer consists of a layer oftantalum pentoxide, with said second layer having a thickness that isapproximately three times greater than a thickness of said first layer.4. The method as recited in claim 3 wherein said layer of silicondioxide has a thickness in the range of 30 to 50 Å and said layer oftantalum pentoxide has a thickness in the range of 90 to 150 Å.
 5. Themethod as recited in claim 1 wherein forming said first electrodefurther includes depositing a layer of phosphorous rich oxide glass. 6.The method as recited in claim 1 wherein forming said second electrodefurther includes forming said conductive layer from material selectedfrom a group consisting of aluminum, chromium, copper, titanium,titanium nitride and titungsten.
 7. The method as recited in claim 1further including forming a via extending from said first electrode andthrough said multi-layer dielectric material, with forming said secondelectrode further including depositing said additional conductive layeradjacent to said multi-layer dielectric film and said via and etchingsaid additional conductive layer to form said second electrode and acontact, with said contact extending from said via, defining acapacitive structure.
 8. The method as recited in claim 7 furtherincluding depositing a layer of Benzocyclobutene (BCB) adjacent to saidcapacitive structure and forming first and second throughways in saidlayer of BCB, with said first throughway extending to said secondelectrode and said second throughway extending to said contact andforming a first metal interconnect to extend in said first throughway tobe in electrical communication with said second electrode and forming asecond metal interconnect to extend in said second throughway to be inelectrical communication with said contact.
 9. A method formanufacturing a capacitor on a semiconductor substrate, said methodcomprising: forming a first electrode by depositing a conductive layeron said substrate; growing, adjacent to said first electrode, a silicondioxide layer by thermal oxidation of the silicon substrate; forming atantalum pentoxide layer adjacent to said silicon dioxide layer bysputter deposition of tantalum to form a tantalum layer in an oxygenrich environment; and forming a second electrode by depositing anadditional conductive layer adjacent to said tantalum containing layer.10. The method as recited in claim 9 wherein said first layer consistsof a layer of silicon dioxide and said second layer consists of a layerof tantalum pentoxide, with said second layer having a thickness that isapproximately three times greater than a thickness of said first layer.11. The method as recited in claim 10 wherein said layer of silicondioxide has a thickness in a range of 30 to 50 Å and said [layer of]tantalum pentoxide has a thickness in a range of 90 to 150 Å.
 12. Themethod as recited in claim 11 wherein forming said first electrodefurther includes growing a layer of phosphorus rich glass composed ofsilicon, phosphorus, and oxygen.
 13. The method as recited in claim 12wherein forming said second electrode further includes forming saidconductive layer from material selected from a group consisting ofaluminum, chromium, copper, titanium, titanium nitride and titungsten.14. The method as recited in claim 13 further including forming a viaextending from said first electrode and through said multi-layerdielectric material, with forming said second electrode furtherincluding depositing said additional conductive layer adjacent to saidmulti-layer dielectric film and said via and etching said additionalconductive layer to form said second electrode and a contact, with saidcontact extending from said via, defining a capacitive structure. 15.The method as recited in claim 14 further including depositing a layerof Benzocyclobutene (BCB) adjacent to said capacitive structure andforming first and second throughways in said layer of BCB, with saidfirst throughway extending to said second electrode and said secondthroughway extending to said contact and forming a first metalinterconnect to extend in said first throughway to be in electricalcommunication with said second electrode and forming a second metalinterconnect to extend in said second throughway to be in electricalcommunication with said contact.
 16. A thin film capacitor formed on asubstrate, said capacitor comprising: first and second spaced-apartconductive films formed on said substrate; and a multi-layer dielectricfilm including first and second layers disposed between said first andsecond conductive films, with said first layer containing silicon andsaid second layer containing tantalum, said first layer being disposedbetween said second layer and said first conductive film and having aroughness associated therewith that is less than a roughness associatedwith said second layer and a thickness sufficient to reduce pin holeformation between said second layer and said first conductive film. 17.The capacitor as recited in claim 16 wherein said first layer consistsof silicon dioxide (SiO₂) and said second layer consists of a tantalumpentoxide (Ta₂O₅), with said second layer having a thickness that isapproximately three times greater than a thickness of said first layer.18. The capacitor as recited in claim 16 wherein said first layerconsists of silicon dioxide (SiO₂) and said second layer consists of atantalum pentoxide (Ta₂O₅), said layer of silicon dioxide having athickness in the range of 30 to 50 Å and said layer of tantalumpentoxide having a thickness in the range of 90 to 150 Å.
 19. Thecapacitor as recited in claim 16 wherein said first conductive filmconsists of diffused phosphorus in silicon and said second conductivefilm includes materials selected from a group consisting of aluminum,chrome, copper, titanium, titanium nitride and titungsten.
 20. Thecapacitor as recited in claim 16 further including a layer ofBenzocyclobutene (BCB), adjacent to said second conductive film, havingfirst and second throughways in said layer of BCB, with said firstthroughway extending to said second electrode and said second throughwayextending to said contact, a first metal interconnect, extending throughsaid first throughway and in electrical communication with said secondelectrode, a second metal interconnect, extending through said secondthroughway and in electrical communication with said contact.